Nanotube structure based metal damascene process

ABSTRACT

In various embodiments a method for manufacturing a metallization layer on a substrate is provided, wherein the method may include forming a plurality of groups of nanotubes over a substrate, wherein the groups of nanotubes may be arranged such that a portion of the substrate is exposed and forming metal over the exposed portion of the substrate between the plurality of groups of nanotubes.

RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.14/168,025, entitled “NANOTUBE STRUCTURE BASED METAL DAMASCENE PROCESS”,filed on Jan. 30, 2014, which is incorporated herein by reference in itsentirety.

TECHNICAL FIELD

Various embodiments relate to a damascene process based on nanotubestructures, for example carbon nanotube (CNT) structures.

BACKGROUND

To overcome the need for better thermal and electrical conductivity insemiconductor manufacturing, metals offering better electrical andthermal conductivity such as copper are increasingly used to replacemetals with lower conductivity such as aluminium for powermetallization. The major hurdle on this way is the structuring of thepower metal in FEOL (front end of line) as well as BEOL (back end ofline) processes. Metals such as copper cannot be structured usingconventional methods (wet or dry etch) due to unavailability of properetching agents. Therefore, at present stage, during provision of powermetallization, metals are structured by a method called dual Damascene,in which a semiconductor workpiece is patterned with open trenches e.g.formed in an oxide layer which are then filled with a thick layer ofmetal, typically copper, usually overfilling the trenches, andchemical-mechanical planarization (CMP) is used to remove the excessportions of the metal. In order to do so, thicker photo resist or oxidelayers, e.g. in the range of 10 μm or more, are used for the structuringprocess of the metal. The larger thickness of photo resist and itsstructuring leads to higher costs and, in addition, technical problemswith photolithography and resist strips may arise. Furthermore, whencopper structures as thick as 50 μm are needed, that conventionalmanufacturing process reaches its application limit.

SUMMARY

In various embodiments a method for manufacturing a metallization layeron a substrate is provided, wherein the method may include forming aplurality of groups of nanotubes over a substrate, wherein the groups ofnanotubes may be arranged such that a portion of the substrate isexposed and forming metal over the exposed portion of the substratebetween the plurality of groups of nanotubes.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings, like reference characters generally refer to the sameparts throughout the different views. The drawings are not necessarilyto scale, emphasis instead generally being placed upon illustrating theprinciples of the invention. In the following description, variousembodiments of the invention are described with reference to thefollowing drawings, in which:

FIGS. 1A to 1H show a method for manufacturing a metallization layer ona substrate according to various embodiments;

FIGS. 2A to 2D show a method for manufacturing a metallization layer ona substrate according to various further embodiments;

FIG. 3 shows a flow chart describing the process flow of the method formanufacturing a metallization layer on a substrate according to variousfurther embodiments; and

FIG. 4 shows a semiconductor device according to various embodiments.

DESCRIPTION

The following detailed description refers to the accompanying drawingsthat show, by way of illustration, specific details and embodiments inwhich the invention may be practiced.

The word “exemplary” is used herein to mean “serving as an example,instance, or illustration”. Any embodiment or design described herein as“exemplary” is not necessarily to be construed as preferred oradvantageous over other embodiments or designs.

In various embodiments of the method described herein, nanotubes, forexample carbon nanotubes (CNTs) may be used to form open trenches intowhich a metal, for example copper, may be filled or deposited. Inaccordance with exemplary embodiments of the method, highly alignedCNTs, also referred to as CNT forest, may be grown directly on thesubstrate on which the power metallization is to be provided. Inaccordance with further exemplary embodiments, an agglomeration ofalready highly aligned CNTs may be grown on a separate substrate and/orin a separate process and be then transferred onto the substrate onwhich the power metallization is to be provided. The nanotube forest maybe structured first and then filled with an electrically insulatingmaterial or it may be filled with an electrically insulating materialand then structured. In the following, the electrically insulatingmaterial will be referred to as insulating material. In both cases, astructured nanotube forest is obtained which includes negative sites,i.e. sites where the nanotubes have been removed thereby defining apattern of trenches. The negative sites when filled with a metal, e.g.copper, may be used as electrical interconnects between a redistributionlayer and devices formed within the substrate. The insulating materialmay be an oxide (e.g. silicon oxide or titanium oxide) or siliconnitride to name a few examples and, when deposited between thenanotubes, may form structures with an electrical resistance in therange of Megaohms. The depth of the negative sites defined by the heightof the nanotubes surrounding those may be adjusted by tuning the growthtime of the nanotubes. In the temperature range from approximately 300°C. to approximately 750° C. a vertical growth in the range fromapproximately 30 μm to approximately 40 μm per minute may be achieved.Therefore, the thickness of the power metal deposited in the negativesites the depth of which is defined by the height of the nanotubes maybe tuned over a wide range from a few micrometers up to a fewmillimeters.

Although CNTs may be seen as the most prominent example of nanotubes,there are numerous other 1D nanomaterials which can be grown in asimilar fashion to CNTs to obtain forests of highly aligned nanotubes ornanowires, such as silicon, gallium nitride (GaN), gallium arsenide(GaAs), oxides such as zinc oxide (ZnO), iron oxide (Fe2O3) etc, and maythus be used in various embodiments. However, up to now the growth andthe structure of CNTs has been well researched such that CNTs can begrown to a very high aspect ratio of approximately 20:1 or more, therebyenabling their usage for the application as described herein. In thisspecification the term “highly aligned” as used herein with respect tonanotubes or nanowires which are 1D structures may be understood to meanthat a majority of nanotubes or nanowires from a group of nanotubes ornanowires may be substantially oriented in the same direction. Forexample, nanotubes or nanowires may be highly aligned in the sense thatthey may be arranged on a surface of a substrate and extend therefrom insubstantially the same direction, i.e. substantially at the same angle(inclination angle) with respect to the surface they are arranged on,wherein the inclination angle may be approximately 90° with deviationsof up to a few degrees from the vertically upright position still beingacceptable. The deviation of the inclination angle from 90° fornanowires or nanotubes other than CNTs (such as ZnO, SnO₂, SiNW etc.)may be larger than for CNTs and may be largely dependent on the growthprocess, substrate orientation etc. The high alignment of a majority ofnanotubes/nanowires from a group may facilitate deposition of theinsulating material therebetween and serve as a stabilizing matrix forthe insulating material. The term “forest” as used herein with respectto nanotubes or nanowires may be understood to mean a dense arrangementof highly aligned nanotubes or nanowires on a surface, wherein thedensity may lie in the range from approximately 10¹¹ nanotubes persquare centimeter to approximately 10¹³ nanotubes per square centimeter.

FIGS. 1A to 1H show a method manufacturing a metallization layer on asubstrate according to various embodiments by using a forest of highlyaligned nanotubes.

In FIG. 1A a substrate 100 is shown on which a metallization layer is tobe provided. The term metallization layer as used herein may be, forexample, understood to mean a layer which may be a structured layerwhich may include a metal a metal stack including a bilayer or amultilayer of different metals or a metal alloy. The substrate 100 maybe a semiconductor substrate which has been processed in FEOL.Therefore, the substrate 100 may include individual devices such astransistors, capacitors, resistors, etc. which may be provided in thesemiconductor in the form of differently doped regions.

FIG. 1B shows the substrate 100 which has been further processed. Afirst layer 102 which may include aluminium, tantalum or tungsten isprovided on the substrate 100. The first layer 102 may have a thicknessin the range from approximately a few tens of nanometers toapproximately a few micrometers. A second layer 104 which may includeiron, cobalt, nickel or any one of the rare earth metals is provided onthe first layer 102. The second layer 104 may have a thickness in therange from approximately 0.5 nm to approximately 3 nm. The first layer102 and the second layer 104 form a catalyst system which enables thegrowth or attachment of nanotubes, for example CNTs on the substrate100. In a sense the composite catalyst system including the first layer102 and the second layer 104 may be seen as a mediating layer in theprocess of growing or attaching nanotubes/nanowires on or to the surfaceof the substrate 100. In this exemplary embodiment, the catalyst systemincludes two layers and is therefore multi-metallic. However, thecatalyst system may only include one of the layers shown in FIG. 1B andtherefore be mono-metallic. The stack including the first layer 102 andthe second layer 104 may be seen as a monolayer and/or multilayer stackof different metals which may support the growth of nanotubes such asCNTs on the surface of the substrate 100 and it may further serve aselectrical contact which may enable metal deposition after the nanotubegrowth process.

In FIG. 1C, a multitude of nanotubes 106 are provided on the substrate100 forming a forest of nanotubes 108. The substrate 100 with thecatalyst system including the two layers 102, 104 being provided thereonmay be heated to temperatures in the range from approximately 300° C. toapproximately 750° C. in order to transform the second layer 104 intocatalyst nano-particles which serve as seed cells for the subsequentgrowing of nanotubes. The growth of nanotubes/nanowires, for exampleCNTs, is a process well known in the state of the art and will not bedescribed within the scope of this specification. Suffice it to say thatthe nanotubes/nanowires 106 may be grown on the substrate 100 by meansof chemical vapour deposition (CVD), for example by ordinary CVD, plasmaenhanced CVD (PECVD) or low pressure CVD (LPCVD). Within the scope ofthis specification the terms nanotubes and nanowires may be usedinterchangeably as they may be seen to be equivalent in the sense thatboth are substantially one-dimensional structures with very high aspectratios which may be provided on surfaces in arbitrary patterns.

Alternatively, the nanotubes 106 may be grown in a separate process on aseparate substrate and be than transferred onto the substrate 100. Inthat case, an undercoating or an adhesion promoting layer for attachingthe nanotubes to the substrate 100 instead of the catalyst system may bedeposited on the substrate 100 which may include soldering paste, silverpaste or a tin alloy. This alternative way of manufacturing thenanotubes 106 separately from the substrate 100 may be favourable if,for some reason for example, the substrate 100 may not be exposed totemperature ranges required for the growing process of the nanotubes.

In FIG. 1D the substrate 100 after a further process stage of themanufacturing of a metallization layer on a substrate is shown. Afterthe forest of nanotubes 108 has been provided on the substrate 100either by growth thereon or by transfer of readily grown nanotubesthereto, an insulating material 110 may be deposited on the forest ofnanotubes 108. The insulating material 110 may include any oxide (e.g.silicon oxide or titanium oxide) or silicon nitride to name a fewexamples. During the deposition of the insulating material 110 it maysettle between the individual nanotubes 106 and may fill the spacewithin the forest of nanotubes 108 from the surface of the substrate 100(e.g. the top surface of the first layer 102 or a correspondingundercoating layer) at least to a plane defined by the free standing endtips of the nanotubes 106. The nanotubes 106 which are covered in theinsulating material 110 form an insulator-nanotube composite 116.

FIG. 1E shows the substrate 100 with the insulator-nanotube composite116 which has been structured into several portions or segments. Thatis, the insulator-nanotube composite 116 from FIG. 1D has been patternedto reveal void sites, i.e. sites where nanotubes 106 together with theinsulating material 110 in their immediate vicinity have been removedsuch that trenches 112 (or gaps) are formed. In other words, a pluralityof groups 116 of nanotubes containing insulating material 110therebetween are formed from the insulator-nanotube composite 116provided over the substrate 100, wherein the plurality of groups 116 ofnanotubes are arranged such that portions of the substrate 100 becomeexposed thereby defining the trenches 116 or negative voids. Theunpatterned nanotube forest 108 containing the insulator material 110,i.e. the insulator-nanotube composite 116, may be etched by means of aproper mask disposed on top of the insulator-nanotube composite 116, forexample by plasma etching. In other words, nanotubes 106 and theinsulating material 110 immediately surrounding those may be removedfrom the insulator-nanotube composite 116 such that the upper surface ofthe substrate 100 is exposed. The depth of the thus created trenches 112may be defined by the height of the nanotubes 106 forming the forest ofnanotubes 108. Compared with the remaining nanotubes 106, the trenchesmay be seen to form negative voids within the insulator-nanotubecomposite 116.

FIG. 1F shows the structure from FIG. 1D after a metal 114 has beenfilled into the negative voids 112, i.e. between portions of theinsulator-nanotube composite 116. The metal 114, for example copper, maybe filled into the trenches 112 by means of electrochemical deposition(ECD).

FIG. 1G shows the structure from FIG. 1F after the insulator-nanotubecomposite portions 116 have been removed, for example by means of a dryetch using oxygen plasma. However, in alternative embodiments theinsulator-nanotube composite portions 116 may remain in place asinsulating pillars between the portions of metal 114 provided within thetrenches 112 in cases where a short circuit caused by the first layer102 and/or the second layer 104 provided under the insulator-nanotubecomposite portion 116 between two corresponding portions of metal 114would not render the corresponding device inoperable, such as in caseswhere two or more portions of metal 114 form or belong to one commonsource/drain contact.

In FIG. 1H the structure from FIG. 1G is shown after the catalyst systemwhich is provided underneath the removed portions of theinsulator-nanotube composite 116 has been removed to avoid the risk ofshort circuits between the adjacent portions of metal 114 formed in theformerly present trenches 112.

An alternative embodiment of the method for manufacturing ametallization layer on a substrate by using a forest of highly alignednanotubes is shown in FIGS. 2A to 2D. As the alternative embodiment tobe described is similar to the one already described with reference toFIGS. 1A to 1H, the same reference numbers will be used for the sameelements and they will not be described again.

As shown in FIG. 2A, the manufacturing method starts with a substrate100 which may correspond to the substrate shown in FIG. 1A.

In FIG. 2B the substrate 100 is shown to be covered with the catalystsystem including the first layer 102 and the second layer 104, however,in a structured manner. To be more precise, here the catalyst system isprovided in the form of discrete catalyst system portions 200 which areinterspaced by gaps 202 where the catalyst system has been removed suchthat the surface of the substrate 100 is exposed. The patterned form ofthe catalyst system may be obtained from the structure as shown in FIG.1B by etching the first layer 102 and the second layer 104 in acorresponding pattern.

As shown in FIG. 2C, the structured catalyst system leads to astructured or patterned growth of nanotubes 106, whereas in the case ofthe manufacturing process described with respect to FIGS. 1A to 1H thecatalyst system is unstructured such that the growth of nanotubes 106thereon is not structured or patterned considering their lateraldistribution on the substrate 100. The growth of nanotubes in that caseconsidering their spatial distribution on the substrate 100 is uniformand therefore not revealing any patterns. In FIG. 2C the nanotubes 106are arranged in groups 204, wherein each group 204 is grown on acatalyst system portion 200. As mentioned above, nanotubes may be alsotransferred onto a structured undercoating layer from a differentsubstrate where they have been grown instead of being grown on thecatalyst system of the substrate 100 to obtain the structure shown inFIG. 2C. The previously formed gaps 202 in the catalyst system includingthe first layer 102 and the second layer 104 may define the position andthe cross-sectional area of the bottom surface of the trenches 112.

In a further process step, the insulating material 110 is deposited overthe substrate 100 such that it may settle between the nanotubes 106within each of the insulator-nanotube composite portions 116. Theinsulating material 110 may be selectively deposited on and around thenanotubes 106 from a gas phase as they will act as nucleation sites foroxide deposition from the gas phase. However, a thin layer of insulatingmaterial 106 with a thickness of a few nanometers may be depositedwithin the trenches 112 which may have to be etched away after thedepositing process The resulting structure is shown in FIG. 2D whichcorresponds to the structure as shown in FIG. 1E. Therefore, comparingthe two embodiments of the method for manufacturing a metallizationlayer on a substrate as described above, the catalyst system may bestructured beforehand such that the nanotubes 106 are grown or arearranged on the substrate 100 in a patterned or structured manner inform of insulator-nanotube composite portions, or the catalyst systemmay remain unstructured which necessitates etching of theinsulator-nanotube composite 116 to obtain the same patterned structureof insulator-nanotube composite portions. Further process steps asdescribed with reference to FIGS. 1F to 1H may performed on thestructure shown in FIG. 2D.

The advantage of both embodiments of the manufacturing process leadingto a (structured) metallization layer on the substrate 100 as describedwith reference to FIGS. 1A to 1H and FIGS. 2A to 2D may be seen in theeasy structuring of the nanotube forest 108. The simple structuring ofthe catalyst system before growing or transferring the nanotubes 106onto the substrate 100 may be used to form complicated trench patternswhile the desired height of the nanotube forest or block portionsthereof is linearly dependent on its growth time. Thus, the height H ofmetal 114 portions as shown in FIG. 1H may be adjusted from a fewmicrometers up to a few to millimeters.

It is to be pointed out that the deposition of the insulating material110 onto and between the nanotubes 106 is an optional step. The twodescribed embodiments of the method for manufacturing a metallizationlayer on a substrate may be executed without employing the insulatingmaterial 106 in the process and hence omitting the instantaneousembodiments shown in FIGS. 1E and 2D. The ensuing etching of theinsulator-nanotube composite 116 (see FIG. 1F) is then replaced by theetching of the forest of nanotubes 106 into separate portions or groupsof nanotubes. In other words, the presence of the insulating material110 does not affect the etching of the forest of nanotubes 108 intoportions or groups of nanotubes or the functionality of the groups ofnanotubes 106 as forming material in order to provide the trenches 112into which metal 114 is filled into. However, if the insulating material110 is left out from the manufacturing process and thenanotubes/nanowires are electrically conductive, then they may be seenas sacrificial structures which may need to be removed in order to avoidshort circuits between the individual portions of metal 114. If theinsulating material 110 is deposited at least between the nanotubes toform the insulator-nanotube composite 116, the individual portionsthereof may remain in place, as the insulating material 110 rendersthose portions of insulator-nanotube composite electricallynonconducting.

In FIG. 3 a flow chart 300 is shown describing the process flow of themethod for manufacturing a metallization layer on a substrate accordingto various further embodiments. In a first step 302, a plurality ofgroups of nanotubes may be formed over a substrate, wherein theplurality of groups of nanotubes are arranged such that a portion of thesubstrate is exposed. In a second step 304, metal may be formed over theexposed portion of the substrate or filled into a trench formed betweenthe plurality of groups of nanotubes. The method as described based onthe flow chart 300 may include further steps in accordance with theaspects described above with reference to FIGS. 1A to 1H and 2A to 2D.

In FIG. 4 a semiconductor device 400 according to various embodiments isshown. The semiconductor device 400 according to various embodiments mayinclude a substrate 402. Over the substrate 402, a plurality of groups404 of nanotubes may be arranged plurality of groups of nanotubesarranged over the substrate 402 and metal 406 may be formed over thesubstrate 402 between the plurality of groups of nanotubes. Thesemiconductor device 400 according to various embodiments may includefurther features in accordance with the aspects described above withreference to FIGS. 1A to 1H and 2A to 2D.

In accordance with various embodiments a method for manufacturing ametallization layer on a substrate is provided, wherein the method mayinclude forming a plurality of groups of nanotubes over a substrate,wherein the groups of nanotubes are arranged such that a portion of thesubstrate is exposed and forming metal over the exposed portion of thesubstrate between the plurality of groups of nanotubes.

According to further embodiments of the method, each group of nanotubesmay include insulating material between the nanotubes.

According to further embodiments of the method forming the plurality ofgroups of nanotubes over a substrate may include depositing a catalystmaterial on the substrate.

According to further embodiments of the method, the catalyst materialmay include a first layer of material, the material being one ofaluminium, tantalum, nickel, titanium, chromium, iron or its alloys(such as Fe—Ni and Fe—Mo, for example) and tungsten.

According to further embodiments of the method the catalyst material mayinclude a second layer of material provided over the first layer ofmaterial, the material of the second layer being one of iron, cobalt andnickel.

According to further embodiments of the method forming the plurality ofgroups of nanotubes over a substrate may include removing a multitude ofnanotubes together with insulating material deposited therebetween froma uniform arrangement of nanotubes with insulating material depositedtherebetween.

According to further embodiments the method may further include growinga uniform arrangement of nanotubes on the surface of the catalystmaterial.

According to further embodiments the method may further include formingan adhesion promoting layer on the substrate; and transferring fullygrown nanotubes from another substrate onto the adhesion promotinglayer.

According to further embodiments the method may further include removingthe catalyst material from underneath the multitude of nanotubes whichhave been removed together with insulating material depositedtherebetween.

According to further embodiments of the method the plurality of groupsof nanotubes may include carbon nanotubes.

According to further embodiments of the method removing the multitude ofnanotubes together with insulating material deposited therebetween mayinclude a plasma etch process.

According to further embodiments of the method the forming of theplurality of groups of nanotubes over a substrate may include depositinga structured layer of catalyst material on the substrate.

According to further embodiments the method may further include growinga uniform arrangement of nanotubes on the surface of the structuredlayer of catalyst material.

According to further embodiments the method may further includestructuring the adhesion promoting layer; and transferring fully grownnanotubes from another substrate onto the structured adhesion promotinglayer.

According to further embodiments of the method the nanotubes in theplurality of groups of nanotubes arranged over the substrate aresubstantially extending at right angle with respect to the substrate.

In accordance with various embodiments a semiconductor device isprovided, wherein the semiconductor device may include a substrate; aplurality of groups of nanotubes which may be arranged over thesubstrate such that a portion of the substrate is exposed; and metalwhich may be formed over the exposed portion of the substrate betweenthe plurality of groups of nanotubes.

According to further embodiments of the semiconductor device each groupof nanotubes may include insulating material between the nanotubes.

According to further embodiments of the semiconductor device theplurality of groups of nanotubes may include carbon nanotubes. Invarious embodiments, the term nanotubes may encompass any other 1Dstructures such as nanowires, nanofibers, nanotubes, microwires,microfibers and microtubes.

While the invention has been particularly shown and described withreference to specific embodiments, it should be understood by thoseskilled in the art that various changes in form and detail may be madetherein without departing from the spirit and scope of the invention asdefined by the appended claims. The scope of the invention is thusindicated by the appended claims and all changes which come within themeaning and range of equivalency of the claims are therefore intended tobe embraced.

What is claimed is:
 1. A semiconductor device comprising: a substrate; aplurality of groups of nanotubes arranged over the substrate; metalformed over the substrate between the plurality of groups of nanotubes.2. The semiconductor device of claim 1, wherein each group of nanotubescomprises insulating material between the nanotubes.
 3. Thesemiconductor device of claim 2, wherein the insulating material extendsfrom a top end to a bottom end of the nanotubes.
 4. The semiconductordevice of claim 1, wherein the metal is formed directly on thesubstrate.
 5. The semiconductor device of claim 1, wherein each of theplurality of groups of nanotubes is aligned substantially verticallyupright with respect to a surface of the substrate.
 6. The semiconductordevice of claim 5, wherein each of the plurality of groups of nanotubeshas substantially the same height from the surface of the substrate. 7.The semiconductor device of claim 6, wherein a top surface of the metalis at approximately a same height level as the plurality of groups ofnanotubes.
 8. The semiconductor device of claim 1, wherein the pluralityof groups of nanotubes comprise carbon nanotubes.
 9. The semiconductordevice of claim 1, further comprising: a first layer provided on thesubstrate; and a second layer provided on the first layer, wherein theplurality of groups of nanotubes are disposed over the second layer. 10.The semiconductor device of claim 9, wherein the first layer comprisesaluminum, tantalum, or tungsten.
 11. The semiconductor device of claim9, wherein the second layer comprises iron, cobalt, nickel, or a rareearth metal.
 12. The semiconductor device of claim 2, wherein theinsulating material comprises an oxide or a silicon nitride.
 13. Thesemiconductor device of claim 12, wherein the oxide is silicon oxide ortitanium oxide.
 14. The semiconductor device of claim 1, wherein themetal formed over the substrate between the plurality of groups ofnanotubes is copper.